CN104610794A - Phosphor-nitrogen intumescent flame retardant, and synthetic method and applications thereof - Google Patents

Phosphor-nitrogen intumescent flame retardant, and synthetic method and applications thereof Download PDF

Info

Publication number
CN104610794A
CN104610794A CN201310535798.5A CN201310535798A CN104610794A CN 104610794 A CN104610794 A CN 104610794A CN 201310535798 A CN201310535798 A CN 201310535798A CN 104610794 A CN104610794 A CN 104610794A
Authority
CN
China
Prior art keywords
fire retardant
nitrogen
phosphorus
agent
paint
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201310535798.5A
Other languages
Chinese (zh)
Other versions
CN104610794B (en
Inventor
汪志勇
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Institute of Advanced Technology University of Science and Technology of China
Original Assignee
Institute of Advanced Technology University of Science and Technology of China
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Institute of Advanced Technology University of Science and Technology of China filed Critical Institute of Advanced Technology University of Science and Technology of China
Priority to CN201310535798.5A priority Critical patent/CN104610794B/en
Priority to US15/032,537 priority patent/US10301548B2/en
Priority to PCT/CN2014/078258 priority patent/WO2015062257A1/en
Priority to JP2016550914A priority patent/JP6338681B2/en
Publication of CN104610794A publication Critical patent/CN104610794A/en
Application granted granted Critical
Publication of CN104610794B publication Critical patent/CN104610794B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K21/00—Fireproofing materials
    • C09K21/06—Organic materials
    • C09K21/12—Organic materials containing phosphorus
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
    • B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
    • B27K3/00—Impregnating wood, e.g. impregnation pretreatment, for example puncturing; Wood impregnation aids not directly involved in the impregnation process
    • B27K3/52—Impregnating agents containing mixtures of inorganic and organic compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/05—Alcohols; Metal alcoholates
    • C08K5/053—Polyhydroxylic alcohols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
    • C08K5/3477—Six-membered rings
    • C08K5/3492—Triazines
    • C08K5/34922—Melamine; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
    • C09D167/08—Polyesters modified with higher fatty oils or their acids, or with natural resins or resin acids
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/18—Fireproof paints including high temperature resistant paints
    • C09D5/185—Intumescent paints
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/48—Stabilisers against degradation by oxygen, light or heat
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
    • D06M13/144—Alcohols; Metal alcoholates
    • D06M13/148—Polyalcohols, e.g. glycerol or glucose
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/244—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus
    • D06M13/282—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus with compounds containing phosphorus
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
    • D06M13/35—Heterocyclic compounds
    • D06M13/355—Heterocyclic compounds having six-membered heterocyclic rings
    • D06M13/358—Triazines
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
    • D06M13/44—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen containing nitrogen and phosphorus
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/03—Non-macromolecular organic compounds
    • D21H17/05—Non-macromolecular organic compounds containing elements other than carbon and hydrogen only
    • D21H17/07—Nitrogen-containing compounds
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/03—Non-macromolecular organic compounds
    • D21H17/05—Non-macromolecular organic compounds containing elements other than carbon and hydrogen only
    • D21H17/10—Phosphorus-containing compounds
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20—Macromolecular organic compounds
    • D21H17/21—Macromolecular organic compounds of natural origin; Derivatives thereof
    • D21H17/24—Polysaccharides
    • D21H17/25—Cellulose
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20—Macromolecular organic compounds
    • D21H17/21—Macromolecular organic compounds of natural origin; Derivatives thereof
    • D21H17/24—Polysaccharides
    • D21H17/28—Starch
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/71—Mixtures of material ; Pulp or paper comprising several different materials not incorporated by special processes
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
    • D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
    • D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
    • D21H21/34—Ignifugeants
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0066—Flame-proofing or flame-retarding additives
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/02—Natural fibres, other than mineral fibres
    • D06M2101/04—Vegetal fibres
    • D06M2101/06—Vegetal fibres cellulosic

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Textile Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Emergency Medicine (AREA)
  • Inorganic Chemistry (AREA)
  • Forests & Forestry (AREA)
  • Fireproofing Substances (AREA)
  • Paints Or Removers (AREA)
  • Laminated Bodies (AREA)

Abstract

The invention provides a phosphor-nitrogen intumescent flame retardant. The phosphor-nitrogen intumescent flame retardant comprises a flame retardant main body; and the flame retardant main body is obtained via reaction of a phosphorization agent, a second nitrogen-containing foaming agent, a second charring agent, and a hydroxyl multi-functional group-containing cross-linking agent. The phosphor-nitrogen intumescent flame retardant is mainly used for flame resisting of paper and cotton fabric. The phosphor-nitrogen intumescent flame retardant is obtained via uniform mixing of the flame retardant main body with other nitrogen-containing foaming agents and charring agents at different ratio, and crushing into nano-micron scale. The nano-micron scaled phosphor-nitrogen intumescent flame retardant is mixed with a paint at a weight ratio of 15 to 30%, so that the paint can be changed into a flame retardant paint capable of maintaining paint mechanical and physical properties. The phosphor-nitrogen intumescent flame retardant possesses phosphor nitrogen synergy effects.

Description

Phosphorus-nitrogen expanding fire retardant, its synthetic method and application thereof
Technical field
The present invention relates to phosphorus-nitrogen expanding fire retardant, its synthetic method and application thereof, and the application of relevant fire retardant in timber, cotton and paper.
Background technology
One of matter of utmost importance of public safety is exactly fire.Along with industrialization degree improves and urbanization range extension, the harm that fire brings is even more serious.In industrially developed country, tilted by the emphasis of fire-fighting from " disappearing " to " preventing ", fire-retardant requirement to be implemented in daily life in the middle of various material.As everyone knows, the fire retardant major part that China is used is at present conventional flame retardant.Although traditional inorganic combustion inhibitor and halogenated flame retardant flame retarding efficiency high, widely applicable, the mechanical and physical performance of the overwhelming majority to base material has obvious detrimentally affect.In addition, there is the secondary harm such as thickness, poisonous or corrosive gases releasing during the combustible material burning of most Halogen sun, serious threat is constituted to environment and personnel safety.Modern society is more and more significant to demand that is efficient, fire retardant.Phosphonium flame retardant has obviously advantage relative to inorganic combustion inhibitor and halogen containing flame-retardant, such as cheap, nontoxic, without metal, to base material applied widely wait clear superiority, become the clear and definite developing direction of present fire retardant industry.Phosphorus-nitrogen expanding fire retardant is the good class sex flame retardant of modern development.It mainly contains acid source (dewatering agent), source of the gas (containing nitrogen blowing agent) and charcoal source (char-forming agent) three part composition.With phosphorus, nitrogen for chief active element, when the plastics adding this based flame retardant are heated, surface energy generates even, the fine and close foam layer of one deck.This foam layer is heat insulation, oxygen barrier, press down cigarette, and can to a certain degree suppress molten drop phenomenon, flame retardant effect is remarkable.It is emphasized that the flame retardant effect of phosphorus-nitrogen expanding fire retardant and the addition of fire retardant have very large relation, after a certain proportion of addition must be reached, just can produce good flame retardant effect.In addition, phosphor-nitrogen expansion type combustion inhibitor must with superpolymer type matching, effectively could produce best flame retardant effect to base material.
Huge and the follow-up social loss of the direct economic loss caused due to fire is very long, and prevention work just becomes more important and urgent, all respects in social life, and that all wishes to accomplish to prevent trouble before it happens is fire-retardant.But, for the oil-base paint often used in building trade and daily life, also there is no respond well fire retardant at present.This is because paint is organic polymer material, not easily fire-retardant.Conventional inorganic combustion inhibitor and halogenated flame retardant interpolation can cause the mechanical and physical performance damage of painting, and as tarnished, water tolerance is looked into, and easily cracks, loss of adhesion etc.So the fire-retardant of paint is the huge challenge of flame retardant area always.As far as our knowledge goes, worldwide only have several patented technology fire-retardant about what paint.The shortcoming that this several fire retardant has some common, as impact paint mechanical and physical performance, halogen-containing, production cost is high.As European patent EP 389, the annular phosphate of 433, cost is high, and technical process is complicated.And be only applicable to minority kind paint.For another example US Patent No. 2010/132332A1, the compatibility of its fire retardant and resin is better, but complex manufacturing, and cost is higher, is mainly used in the fire-retardant of plastics and rubber item, has certain limitation to the scope of application of resin.Rome Leah patent Rom.RO94; 457 formulas once disclosing a kind of fire retarding paint; adopt nonflammable phthalic ester linseed oil as matrix; add the hydrate of ammonium hydrogen phosphate and sodium carbonate as fire retardant; this is a kind of fp linseed oil coating, is not conventional meaning to have corrosion-resistant and paint that is provide protection.Ammonium hydrogen phosphate and sodium carbonate are inorganic salt, and look into the compatibility of paint, the easy moisture absorption, can change the mechanical and physical performance of most of resin.Chinese patent CN101629043A discloses a kind of fireproof flame resistance paint, but this paint is only fire-retardant for ferrous metal surface, and uses high toxicity and highly corrosive compound phosphorus oxychloride in production process.US Patent No. 2004/6686403 uses a certain proportion of trimeric cyanamide, tetramethylolmethane and melamine phosphate are as acid source and charcoal source raw material, formula with forming a kind of fire retarding paint after paint component stirring and evenly mixing, then just can have flame retardant effect through baking vanish program.Thus this patent fails to solve the fire-retardant problem of broad spectrum in various paint equally.Thus fire retardant of the present invention from report other to invent be different, creative.
Summary of the invention
The present invention is directed to phosphorus-nitrogen expanding fire retardant, its synthetic method and application thereof, the method is eco-friendly synthetic method, described fire retardant is in high concentrations of toluene diisocyanate, epoxy resin paints, in the common paint such as alkyd paint, there is fire-retardant application, the problems such as the feel of solution fire retarding wood, cotton, paper is poor and get damp.Reduce the application of existing inorganic combustion inhibitor and halogen flame and the environmental pollution caused thus and the injury to human body simultaneously.
In one embodiment of the invention, a kind of phosphorus-nitrogen expanding fire retardant is provided, described fire retardant comprises fire retardant main body, and described fire retardant main body is obtained containing the reaction of nitrogen blowing agent, the second char-forming agent and hydroxyl polyfunctional crosslinking agent by phosphorization reagent, second.
In one embodiment of the invention, fire retardant also comprises first containing nitrogen blowing agent and the first char-forming agent.
In one embodiment of the invention, the ratio of each composition is with described fire retardant main body: described first containing nitrogen blowing agent: described first char-forming agent counts 1-3: 0.5-1.5: 0.2-1.2.
In one embodiment of the invention, described first can be identical containing nitrogen blowing agent and second containing nitrogen blowing agent also can be different, described first is that physics contains nitrogen blowing agent or chemistry containing nitrogen blowing agent containing nitrogen blowing agent and second containing nitrogen blowing agent independently of one another, and described first is liquid, gas or solid containing nitrogen blowing agent and second containing nitrogen blowing agent independently of one another.
In one embodiment of the invention, described first be selected from independently of one another containing nitrogen blowing agent containing nitrogen blowing agent and second: bicarbonate of ammonia, trimeric cyanamide, poly-phosphamide, urea, Urea,amino-, hydrazine class compound, guanidine compound, azo-compound.
In one embodiment of the invention, described first char-forming agent and the second char-forming agent can be identical also can be different, and/or described first char-forming agent and the second char-forming agent are liquid, gas or solid independently of one another.
In one embodiment of the invention, described first char-forming agent and the second char-forming agent can be selected from independently of one another: amylose starch, amylopectin, cyclodextrin, saccharide compound and polyhydric alcohol amine compounds.
In one embodiment of the invention, described phosphorization reagent is red phosphorus, Vanadium Pentoxide in FLAKES, phosphoric acid, tetra-sodium, polyphosphoric acid, phosphamide, poly-phosphamide or phosphorus oxychloride.
In one embodiment of the invention, described hydroxyl polyfunctional crosslinking agent be ethylene glycol, glycerine, tetramethylolmethane, mesitylene phenol, Resorcinol, monoethanolamine, aminopropanol or alcamine compound.
In one embodiment of the invention, described phosphorization reagent, second containing nitrogen blowing agent, the second char-forming agent and hydroxyl polyfunctional crosslinking agent reaction finally add alkali so that the pH value of reaction solution is adjusted to 5-8.
In one embodiment of the invention, described alkali is mineral alkali or organic bases.
In one embodiment of the invention, described alkali is oxyhydroxide or aminated compounds.
In one embodiment of the invention, described alkali is aqueous methylamine solution, quadrol, triethylamine, aniline, ammoniacal liquor or alcamine compound.
In one embodiment of the invention, the infrared spectra of described phosphorus-nitrogen expanding fire retardant has following characteristics absorption: 3395cm -1, 3231cm -1, 1781cm -1, 1736cm -1, 1536cm -1, 1447cm -1, 1084cm -1, 1020cm -1and 527cm -1.
In one embodiment of the invention, the mass spectrum of described phosphorus-nitrogen expanding fire retardant has following characteristics peak: base peak m/e=263.0, and there is m/e=223.0,247.1,274.3,284.9,318.3,330.4,382.9,404.8,484.8,524.8,626.7 at further feature peak.
In one embodiment of the invention, in the reaction of described phosphorization reagent, second containing nitrogen blowing agent, the second char-forming agent and hydroxyl polyfunctional crosslinking agent, first make described phosphorization reagent and described second react under the existence of initiator containing nitrogen blowing agent, add described second char-forming agent and described hydroxyl polyfunctional crosslinking agent afterwards.
In one embodiment of the invention, initiator is water or alkaline aqueous solution.
In one embodiment of the invention, phosphorization reagent and the described first weight ratio containing nitrogen blowing agent are 1: 0.5 to 1: 4.0.
In one embodiment of the invention, the weight ratio of phosphorization reagent and described first char-forming agent is 1: 0.5 to 1: 3.0.
In one embodiment of the invention, the weight ratio of phosphorization reagent and described hydroxyl polyfunctional crosslinking agent is 1: 0.5 to 1: 4.0.
In one embodiment of the invention, the granular size of fire retardant is 0.4-20.0 micron.
In one embodiment of the invention, the phosphorus content of fire retardant is 8-23%.
In one embodiment of the invention, the nitrogen content of fire retardant is 10-34%.
In one embodiment of the invention, a kind of method preparing phosphorus-nitrogen expanding fire retardant is provided, said method comprising the steps of: a) fire retardant main body preparation process, wherein make phosphorization reagent, second containing nitrogen blowing agent, the second char-forming agent and hydroxyl polyfunctional crosslinking agent reaction, to obtain the reaction system containing fire retardant main body; B) filtration step, wherein leaches the solid in above reaction system and dries, to obtain fire retardant main body; C) mixing step, wherein mixes described fire retardant main body containing nitrogen blowing agent and the first char-forming agent with first.
In one embodiment of the invention, in described fire retardant main body preparation process, first make described phosphorization reagent and described second react under the existence of initiator containing nitrogen blowing agent, add described second char-forming agent and described hydroxyl polyfunctional crosslinking agent afterwards.
In one embodiment of the invention, after described fire retardant main body preparation process and before described filtration step, add alkali so that the pH value of reaction solution is adjusted to 5-8.
In one embodiment of the invention, alkali is mineral alkali or organic bases.
In one embodiment of the invention, alkali is oxyhydroxide or aminated compounds.
In one embodiment of the invention, alkali is aqueous methylamine solution, quadrol, triethylamine, aniline, ammoniacal liquor or alcamine compound.
In one embodiment of the invention, after described filtration step and before described mixing step, also comprise the step of described fire retardant main body drying.
In one embodiment of the invention, in described mixing step, phosphorus-nitrogen expanding fire retardant homogeneous powder is broken to 0.4-20.0 micron.
In one embodiment of the invention, the purposes of phosphorus-nitrogen expanding fire retardant of the present invention in paint is fire-retardant is provided.
In one embodiment of the invention, described phosphorus-nitrogen expanding fire retardant is mixed in paint by the weight ratio of 15-30%.
In one embodiment of the invention, the main ingredient of paint is urethane, epoxy resin, Synolac, urea-formaldehyde resin or resol.
In one embodiment of the invention, provide a kind of fire retarding paint, described fire retarding paint comprises main body paint and phosphorus-nitrogen expanding fire retardant of the present invention.
In one embodiment of the invention, fire retarding paint is 28-35% according to the oxygen index LOI that standard GB/T 5454-85 measures.
In one embodiment of the invention, the mechanical and physical performance of fire retarding paint is up to state standards the indices of GB/T 23997-2009 and GB18581-2009.
In one embodiment of the invention, the purposes of phosphorus-nitrogen expanding fire retardant of the present invention in timber, cotton and paper are fire-retardant is provided.
In one embodiment of the invention, drying is taken out after timber, cotton or paper being soaked in the dispersion liquid of described phosphorus-nitrogen expanding fire retardant.
In one embodiment of the invention, provide a kind of fire retarding wood, described fire retarding wood contains phosphorus-nitrogen expanding fire retardant of the present invention.
In one embodiment of the invention, the oxygen index LOI of fire retarding wood is greater than 40%.
In one embodiment of the invention, provide a kind of flame-retardant cotton, described flame-retardant cotton contains phosphorus-nitrogen expanding fire retardant of the present invention.
In one embodiment of the invention, the oxygen index LOI of flame-retardant cotton is greater than 35%.
In one embodiment of the invention, provide a kind of fire retardant papers, described fire retardant papers contains phosphorus-nitrogen expanding fire retardant.
In one embodiment of the invention, the oxygen index LOI of fire retardant papers is greater than 30%.
In the present invention, a series of phosphorus-nitrogen expanding fire retardant general preparative methods is provided.In one embodiment, the phosphorization reagent of 1 weight part is joined in mixing vessel, then join second of 0.5-4 weight part in mixing vessel containing nitrogen blowing agent under stirring, under room temperature, rapid stirring is to mixing and stirring, adds a certain amount of water initiation reaction subsequently in batches.After above-mentioned reaction completes, add the second char-forming agent of 0.5-3 weight part again in mixing vessel in batches, then the hydroxyl polyfunctional crosslinking agent of 0.5-4 weight part is joined in mixing vessel more in batches, continue stirring and make it react completely.Finally add aminated compounds and control stirring velocity and temperature of reaction, in and pH value be 5-8, then filter or after press filtration, dry and namely obtain phosphorus-nitrogen expanding fire retardant main part.This main part and first to be mixed in (1-3: 0.5-1.5: 0.2-1.2) ratio containing nitrogen blowing agent and the first carbon forming agent and is crushed to and receive micro-meter scale, namely obtain phosphorus-nitrogen expanding fire retardant.By gained filtrate with the dilution of 1/3-2/3 water, namely obtain fire retardant.
Usual phosphor nitrogen combustion inhibitor mainly comprises acid source (dewatering agent), source of the gas (containing nitrogen blowing agent) and charcoal source (char-forming agent) three part.For chief active element, and have mutual promoting action with phosphorus, nitrogen, nitrogen moiety accelerates the dehydration endotherm process of phosphoric acid, the nitrogenous gas that the catalyzed formation of amine moieties is not simultaneously fired.Can carbonization be there is after the catalyzed dehydration of carbon forming agent, form even, fine and close foam layer on surface together with resin.This foam layer is heat insulation, oxygen barrier, press down cigarette, and can to a certain degree suppress molten drop phenomenon, flame retardant effect is remarkable.Adding of poly-hydroxy linking agent not only increases dehydration endotherm effect, facilitates the densification of film and difficult combustion especially, thus effectively improves flame retardant effect.
In one embodiment, phosphorus-nitrogen expanding fire retardant is insoluble in most of organic solvent, is slightly soluble in water; Stable chemical nature, has good compatibility with high molecular polymer, leaves standstill not stratified.
Phosphorus-nitrogen expanding fire retardant of the present invention is applicable to the paint of all kinds and the brand seen in the market.The paint type doing experiment has, polyester and high concentrations of toluene diisocyanate, alkyd paint, and epoxy resin paints, and polyvinyl chloride paints, the high molecular polymers such as quick-drying primer.Paint brand comprises: China Resources board high concentrations of toluene diisocyanate, ippon board polyurethane lacquer, the quick-drying primer of Hefei Li Guang painting company limited and high concentrations of toluene diisocyanate.Phosphorus-nitrogen expanding fire retardant of the present invention 5 grams is added in 20 grams of paint, good flame retardant effect can be reached.Such as inflammable high concentrations of toluene diisocyanate (China Resources board), adds this fire retardant 25% (weight ratio), can obtain the fire retarding paint (annex 5) that oxygen index reaches 30.1%.Its mechanical and physical performance of fire retarding paint after interpolation can reach the property indices of GB/T23997-2009 and GB18581-2009 standard-required.
Concrete mechanical and physical performance is as follows: surface drying≤1 hour; Do solid work≤24 hours; Paint film appearance=normal; Package stability (50 DEG C, 7d)=normal; Sticking power=0 grade; Pencil hardness (scratch) >=2H; Dry heat resistance=1; Wear resistance=0.045; Water tolerance≤24 hour; Alkali resistance≤2 hour; Alcohol resistance≤8 hour; Stain resistance≤1 hour; Volatile organic matter (g/L)=600; Benzene content (%)=0; Toluene, dimethylbenzene, ethyl-benzene level summation (%)=25; Halohydrocarbon content (%=0; Free-diisocyanate content summation (%)=0.1; Lead content (mg/kg)=1; Cadmium content (mg/kg) < 1; Chromium content (mg/kg)=1; Mercury content (mg/kg)=0;
A blank of fire retardant kind filled up by fire retardant of the present invention, and solving fire retardant for a long time cannot be compatible and use paint and do not have a universality problem in paint.Fire retardant of the present invention is added to by a certain percentage in various types of paint, while the decorate properties retaining crude oil paint and other mechanical and physical performance, make paint have the anti-flaming function of similar frie retardant coating.The present invention is compared with existing fire retardant, Halogen, cheap without metal, the prices of raw and semifnished materials, production energy consumption is low, multifunction, on advantages such as the mechanical and physical performance impact of paint matrix are little.As a comparison, most of fire retardant is large on the impact of the mechanical and physical performance of matrix, as red phosphorus, antimonous oxide, aluminium hydroxide adds in cable or polystyrene in the person that makes cable, causes the toughness of matrix and resistance to impact shock to reduce; Poly-phosphamide adds in paint makes paint tarnish, loss of adhesion, and water tolerance lowers; Phosphate compounds adds in paint makes paint layering etc.
Accompanying drawing explanation
Fig. 1: the phosphorus-nitrogen expanding fire retardant Elemental analysis data of embodiment 1, testing tool is XRF-1800X ray fluorescence spectrometer (SHIMADZU company)
Fig. 2: the phosphorus-nitrogen expanding fire retardant particle size distribution data of embodiment 1
Fig. 3: the phosphorus-nitrogen expanding fire retardant mass-spectrometric data of embodiment 1
Fig. 4: the phosphorus-nitrogen expanding fire retardant infrared spectrum of embodiment 1
Fig. 5: the fire retarding paint oxygen index test result of embodiment 1
Fig. 6 a: the fire retarding paint mechanical and physical performance survey report of embodiment 1
Fig. 6 b: the fire retarding paint mechanical and physical performance survey report attached sheet of embodiment 1
Embodiment
Embodiment
Embodiment 1
In 250 ml beakers, add 10 grams of polyphosphoric acid, then add containing nitrogen blowing agent trimeric cyanamide 10 grams in batches, stir, add suitable quantity of water initiation reaction, and make it fully react; Add 6 grams of char-forming agents such as Mierocrystalline cellulose again and continue reaction; Add hydroxyl polyfunctional crosslinking agent again as Resorcinol 10 grams and polyvalent alcohol 5 grams; Question response is complete, is cooled to room temperature, then at 15-40 DEG C of temperature, adds amine, and as in aqueous methylamine solution and pH to 5-8, subsequent filtration, by filter residue oven dry, obtains fire retardant main body.Obtained fire retardant main body and melamine phosphate and tetramethylolmethane are mixed pulverizing in (1-3: 0.5-1.5: 0.2-1.2) ratio, namely obtains phosphor-nitrogen expansion type combustion inhibitor.Gained byproduct filtrate is diluted with 1/3 water, can obtain flame retardant products.
This fire retardant 6 grams is joined in 20 grams of high concentrations of toluene diisocyanate, mixes, use national GB12441-2005 frie retardant coating standard (temporarily without fire retarding paint standard), be coated onto and wooden five-ply board base material obtains fire retarding paint performance be:
Duration of fire resistance is 10 minutes (big panel method);
Flame propagation velocity 38% (combustion tunnel method);
Carbonization volume, weightless 9g (cell combustion method);
Paint bar oxygen index (LOI) 30.1%.
Mechanical and physical performance reaches GB/T23997-2009 and GB18581-2009 standard
Embodiment 2
According to the method described in embodiment 1, keep the consumption of polyphosphoric acid constant, and the value listed by the ratio of wherein polyphosphoric acid and the second carbon forming agent tetramethylolmethane is changed in table 1, carry out above-mentioned experiment.Experimental result provides in Table 1.
Table 1. phosphorization reagent compares experimental result with the Different Weight of hydroxyl polyfunctional crosslinking agent
As can be seen from the above table, the ratio of phosphorization reagent and linking agent all can obtain gratifying result in the scope of 1: 3, and especially outstanding in 1: 2 result.
Embodiment 3
Fire retardant main body flame retardant effect:
Fire retardant main body in embodiment 16 grams is joined in 20 grams of high concentrations of toluene diisocyanate, mixes, use national GB12441-2005 frie retardant coating standard (temporarily without fire retarding paint standard), be coated onto and wooden five-ply board base material obtains fire retarding paint performance be:
Duration of fire resistance is 7 minutes (big panel method);
Flame propagation velocity 50% (combustion tunnel method);
Carbonization volume, weightless 12.5 grams (cell combustion method);
Paint bar oxygen index (LOI) 24.5%.
Embodiment 4
Do not use the comparison of linking agent:
In 250 ml beakers, add 10 grams of polyphosphoric acid, then add containing nitrogen blowing agent trimeric cyanamide 10 grams in batches, stir, add suitable quantity of water initiation reaction, make it fully react; Add 6 grams of char-forming agents again as Mierocrystalline cellulose, fully react, in this process, do not add linking agent.Question response is complete, is cooled to room temperature, then at 15-40 DEG C of temperature, adds amine, and as in aqueous methylamine solution and pH to 5-8, subsequent filtration, dries filter residue.The solid obtained and melamine phosphate and tetramethylolmethane mix pulverizing in (1-3: 0.5-1.5: 0.2-1.2) ratio, obtain pressed powder.This pressed powder 6 grams is joined in 20 grams of high concentrations of toluene diisocyanate, mixes, use national GB12441-2005 frie retardant coating standard (temporarily without fire retarding paint standard), be coated onto and wooden five-ply board base material obtains fire retarding paint performance be:
Duration of fire resistance is 6.5 minutes (big panel method);
Flame propagation velocity 55% (combustion tunnel method);
Carbonization volume, weightless 13 grams (cell combustion method);
Paint bar oxygen index (LOI) 24%.
Embodiment 5
Adopt the method identical with embodiment 4, use linking agents (10 grams) different shown in table 2, the result obtained provides in table 2.
Table 2. adopts identical preparation method, changes the fire retardant experimental data that different linking agents obtains
As can be seen from the above table, multicomponent alcoholics compound all can be used as linking agent and uses in the present invention, and wherein the effect of polyphenol is especially outstanding.
Embodiment 6
Bicarbonate of ammonia compares as whipping agent:
In 250 ml beakers, add 10 grams of polyphosphoric acid, then add 10 grams, whipping agent bicarbonate of ammonia in batches, stir, add suitable quantity of water initiation reaction, make it fully react; Add 6 grams of char-forming agents such as Mierocrystalline cellulose and polyol crosslink agent again to react further.Question response is complete, is cooled to room temperature, then at 15-40 DEG C of temperature, adds amine, and as in aqueous methylamine solution and pH to 5-8, subsequent filtration, dries filter residue.The solid obtained and melamine phosphate and tetramethylolmethane mix pulverizing in (1-3: 0.5-1.5: 0.2-1.2) ratio, obtain pressed powder.This pressed powder 6 grams is joined in 20 grams of high concentrations of toluene diisocyanate, mixes, use national GB12441-2005 frie retardant coating standard (temporarily without fire retarding paint standard), be coated onto and wooden five-ply board base material obtains fire retarding paint performance be:
Duration of fire resistance is 5 minutes (big panel method);
Flame propagation velocity 60% (combustion tunnel method);
Carbonization volume, weightless 14.5 grams (cell combustion method);
Paint bar oxygen index (LOI) 22.0%.
Embodiment 7
Adopt the method identical with embodiment 6, use the whipping agent shown in table 3 10 grams, the result obtained provides in table 3.
Table 3. adopts identical preparation method, changes the fire retardant experimental data that different whipping agents obtains
As can be seen from the above table, amine. compounds all can be used as whipping agent and uses in the present invention, and wherein the effect of amino urine is especially outstanding.
Embodiment 8
Mesitylene phenol compares as carbon forming agent:
In 250 ml beakers, add 10 grams of polyphosphoric acid, then add whipping agent trimeric cyanamide 8 grams in batches, stir, add suitable quantity of water initiation reaction, make it fully react; Add 6 grams of char-forming agent mesitylene phenol again and polyol crosslink agent is reacted further.Question response is complete, is cooled to room temperature, then at 15-40 DEG C of temperature, adds amine, as in aqueous methylamine solution and pH to 5-8, then filters, is dried by filter residue.The solid obtained and melamine phosphate and tetramethylolmethane mix pulverizing in (1-3: 0.5-1.5: 0.2-1.2) ratio, obtain pressed powder.This pressed powder 6 grams is joined in 20 grams of high concentrations of toluene diisocyanate, mixes, use national GB12441-2005 frie retardant coating standard (temporarily without fire retarding paint standard), be coated onto and wooden five-ply board base material obtains fire retarding paint performance be:
Duration of fire resistance is 8 minutes (big panel method);
Flame propagation velocity 46% (combustion tunnel method);
Carbonization volume, weightless 11.5 grams (cell combustion method);
Paint bar oxygen index (LOI) 26.5%.
Embodiment 9
Adopt the method identical with embodiment 8, use the carbon forming agent shown in table 46 grams, the result of acquisition provides in table 4.
Table 4. adopts identical preparation method, changes the fire retardant experimental data that different carbon forming agents obtains
As can be seen from the above table, hydroxy kind compound all can be used as char-forming agent and uses in the present invention, and wherein the effect of trisphenol is especially outstanding.
Embodiment 10
Phosphoric acid compares as phosphorization reagent:
In 250 ml beakers, add 10 grams of phosphoric acid, then add whipping agent trimeric cyanamide 8 grams in batches, stir, add suitable quantity of water initiation reaction, make it fully react; Add 6 grams of char-forming agent Mierocrystalline celluloses again and polyol crosslink agent is reacted further.Question response is complete, is cooled to room temperature, then at 15-40 DEG C, adds amine, as in aqueous methylamine solution and pH to 5-8, then filters, is dried by filter residue.The solid obtained and melamine phosphate and tetramethylolmethane mix pulverizing in (1-3: 0.5-1.5: 0.2-1.2) ratio, obtain pressed powder.This pressed powder 6 grams is joined in 20 grams of high concentrations of toluene diisocyanate, mixes, use national GB12441-2005 frie retardant coating standard (temporarily without fire retarding paint standard), be coated onto and wooden five-ply board base material obtains fire retarding paint performance be:
Duration of fire resistance is 7.5 minutes (big panel method);
Flame propagation velocity 47% (combustion tunnel method);
Carbonization volume, weightless 12.5 grams (cell combustion method);
Paint bar oxygen index (OI) 25.1%.
Embodiment 11
Adopt the method identical with embodiment 10, use the different phosphorization reagents (8-14 gram) shown in table 5, the result of acquisition provides in table 5.
Table 5. adopts same procedure, the experimental data of different phosphorization reagent
As can be seen from the above table, phosphate compound all can be used as phosphorization reagent and uses in the present invention, and wherein the effect of polyphosphoric acid is especially outstanding.
Embodiment 12
Aqueous sodium hydroxide solution is as alkali neutralization ratio comparatively:
In 250 ml beakers, add 10 grams of phosphoric acid, then add whipping agent trimeric cyanamide 8 grams in batches, stir, add suitable quantity of water initiation reaction, make it fully react; Add 6 grams of char-forming agent Mierocrystalline celluloses again and polyol crosslink agent is reacted further.Question response is complete, is cooled to room temperature, then adds in aqueous sodium hydroxide solution and pH to 5-8 at 15-40 DEG C, then filters, dried by filter residue.The solid obtained and melamine phosphate and tetramethylolmethane mix pulverizing in (1-3: 0.5-1.5: 0.2-1.2) ratio, obtain pressed powder.This pressed powder 6 grams is joined in 20 grams of high concentrations of toluene diisocyanate, mixes, use national GB12441-2005 frie retardant coating standard (temporarily without fire retarding paint standard), be coated onto and wooden five-ply board base material obtains fire retarding paint performance be:
Duration of fire resistance is 8 minutes (big panel method);
Flame propagation velocity 45% (combustion tunnel method);
Carbonization volume, weightless 11.5 grams (cell combustion method);
Paint bar oxygen index (OI) 26.5%.
Embodiment 13
Adopt the method identical with embodiment 12, alkali different shown in use table 6 neutralizes neutral (consumption 5-14 gram) to carry out, and the result of acquisition provides in table 6.
Table 6. adopts same procedure, the experimental data of Different Alkali neutralization
As can be seen from the above table, aminated compounds all can in and middle use, and wherein the effect of methylamine is especially outstanding.
Embodiment 14
Neutralization is to the comparison of pH=3 and pH=10:
In 250 ml beakers, add 10 grams of phosphoric acid, then add whipping agent trimeric cyanamide 8 grams in batches, stir, add suitable quantity of water initiation reaction, make it fully react; Add 6 grams of char-forming agent Mierocrystalline celluloses again and polyol crosslink agent is reacted further.Question response is complete, is cooled to room temperature, then at 15-40 DEG C of temperature, adds amine, as in aqueous methylamine solution and pH=3 or pH=10.Neutralization is to a small amount of solid obtained during pH=3 compared with thickness, and the mechanical and physical performance damage of this solid to matrix is comparatively large, is not suitable as fire retardant main body.Neutralization obtains solid to during pH=10.The solid obtained and melamine phosphate and tetramethylolmethane mix pulverizing in (1-3: 0.5-1.5: 0.2-1.2) ratio, obtain pressed powder.This pressed powder 6 grams is joined in 20 grams of high concentrations of toluene diisocyanate, mixes, use national GB12441-2005 frie retardant coating standard (temporarily without fire retarding paint standard), be coated onto and wooden five-ply board base material obtains fire retarding paint performance be:
Duration of fire resistance is 10 minutes (big panel method);
Flame propagation velocity 40% (combustion tunnel method);
Carbonization volume, weightless 10 grams (cell combustion method);
Paint bar oxygen index (OI) 28.8%.
Embodiment 15
The pH value be neutralized in embodiment 14 is changed into the value in table 7, the result obtained provides in table 7.
Table 7. neutralizes the experimental data of different pH
As can be seen from the above table, pH flame retardant effect and reaction yield within the scope of 5-8 reaches optimum balance effect.
Embodiment 16
Fire retardant larger particles compares:
The solid that embodiment 1 obtains is crushed to more than 50 microns sizes, getting 6 grams joins in 20 grams of high concentrations of toluene diisocyanate, mix, use national GB12441-2005 frie retardant coating standard (temporarily without fire retarding paint standard), be coated onto and wooden five-ply board base material obtains fire retarding paint performance be:
Duration of fire resistance is 7.5 minutes (big panel method);
Flame propagation velocity 49% (combustion tunnel method);
Carbonization volume, weightless 12.0g (cell combustion method);
Paint bar oxygen index (OI) 25.6%.
Table 8.
As can be seen from Table 8, the fire retardant of larger particles causes paint mechanical and physical performance to decline, and after paint surface drying, substantially tarnish, sticking power reduces.
Embodiment 17
In 250 milliliters of compact ceramic retort, add 10 grams of tetra-sodiums, then add 8 grams of melamine phosphates in batches, stir, suitable quantity of water initiation reaction, and make it fully react; Add 6 grams of char-forming agent starch again, continue reaction.Add linking agent aminopropanol and char-forming agent tetramethylolmethane subsequently, question response completes and after being cooled to room temperature, then adds in amine and pH to 5-8.This dirty solution is filtered, and the filter residue obtained is dried.Gained solid and first is containing nitrogen blowing agent, and the first carbon forming agent agent mixes in (1-3: 0.5-1.5: 0.2-1.2) ratio, pulverizes, and namely obtains phosphorus-nitrogen series expansion type paint fire retardant.
This fire retardant 7 grams is joined in 20 grams of epoxy resin paint, mix, be coated on corresponding wood substrate plate.Use national GB12441-2005 frie retardant coating standard (temporarily without fire retarding paint standard), the fire retarding paint performance detected is:
Duration of fire resistance is 14 minutes (big panel method);
Flame propagation velocity 31% (combustion tunnel method);
Carbonization volume, weightless 8.0g (cell combustion method);
Paint bar oxygen index (OI) 35%.
Mechanical and physical performance reaches GB/T23997-2009 and GB18581-2009 standard
Embodiment 18
Comparison without the first carbon forming agent:
Fire retardant main body embodiment 10 obtained and first mixes in 1: 1 ratio containing nitrogen blowing agent, pulverizes, and namely obtains not containing the phosphorus-nitrogen series expansion type paint fire retardant of the first carbon forming agent.
This fire retardant 7 grams is joined in 20 grams of epoxy resin paint, mix, be coated on corresponding wood substrate plate.Use national GB12441-2005 frie retardant coating standard (temporarily without fire retarding paint standard), the fire retarding paint performance detected is:
Duration of fire resistance is 9 minutes (big panel method);
Flame propagation velocity 41% (combustion tunnel method);
Carbonization volume, weightless 9.5 grams (cell combustion method);
Paint bar oxygen index (OI) 27.8%.
Embodiment 19
Comparison without the first whipping agent:
Fire retardant main body embodiment 10 obtained and the first carbon forming agent mix in 1: 2 ratio, pulverize, and namely obtain not containing the phosphorus-nitrogen series expansion type paint fire retardant of the first whipping agent.
This fire retardant 7 grams is joined in 20 grams of epoxy resin paint, mix, be coated on corresponding wood substrate plate.Use national GB12441-2005 frie retardant coating standard (temporarily without fire retarding paint standard), the fire retarding paint performance detected is:
Duration of fire resistance is 8.5 minutes (big panel method);
Flame propagation velocity 42% (combustion tunnel method);
Carbonization volume, weightless 10g (cell combustion method);
Paint bar oxygen index (OI) 27.1%.
Embodiment 20
Application in alkyd paint:
Phosphorus embodiment 10 prepared-nitrogen series expansion type paint fire retardant 7 grams joins in alkyd paint, mixes, is coated onto on wooden three-ply-wood base material.Use national GB12441-2005 frie retardant coating standard (temporarily without fire retarding paint standard), recording fire retarding paint performance is:
Duration of fire resistance is 11 minutes (big panel method);
Flame propagation velocity 36% (combustion tunnel method);
Char volume, weightless 8.5 grams (cell combustion method);
Oxygen index (OI) 30%.
Mechanical and physical performance reaches GB/T23997-2009 and GB18581-2009 standard
Embodiment 21
Change fire retardant main body as shown in table 9: the first whipping agent: the first carbon forming agent ratio, (main quality 10 grams), the result obtained provides in table 9.
Table 9. fire retardant main body: the first whipping agent: the first carbon forming agent different ratios experimental data
As can be seen from Table 9, when fire retardant main body: the first whipping agent: provide best oxygen index when the first char-forming agent (weight ratio) ratio is 3: 1: 1.2.
Embodiment 22
The plank of 90 × 190 × 20mm and 190 × 1000 × 20mm is inserted in fire retardant and boils immersion 10 minutes, then take out and dry or dry.Then according to GB 8624-88 canonical measure.Test specimen burning residue length mean value > 150mm, average flue-gas temperature < 200 DEG C.Wood strip oxygen index (OI) > 40% in addition after this process.Plank after this fire retardant process is flame retardancy material of construction.
Embodiment 23
Cotton fabric is put into this fire retardant soak at room temperature 10 minutes, take out and dry or dry.Then GB 8624-2006 canonical measure is pressed.Test specimen is tested through vertical combustion, average after flame time 0 second, on average glows 0 second time, average char length 105mm, and oxygen index (OI) is 37.5%.
The above; only in order to the present invention's preferably embodiment; but protection scope of the present invention is not limited thereto; any those skilled in the art is in the technical scope that the present invention discloses; the change that can expect easily or replacement; all should be encompassed in protection scope of the present invention, therefore, protection scope of the present invention should be as the criterion with the protection domain described in claim.

Claims (10)

1. phosphorus-nitrogen expanding fire retardant, described fire retardant comprises fire retardant main body, and described fire retardant main body is obtained containing the reaction of nitrogen blowing agent, the second char-forming agent and hydroxyl polyfunctional crosslinking agent by phosphorization reagent, second.
2. phosphorus-nitrogen expanding fire retardant according to claim 1, described fire retardant also comprises first containing nitrogen blowing agent and the first char-forming agent.
3. phosphorus-nitrogen expanding fire retardant according to claim 1, wherein said first is selected from containing nitrogen blowing agent independently of one another containing nitrogen blowing agent and second: bicarbonate of ammonia, trimeric cyanamide, poly-phosphamide, urea, Urea,amino-, hydrazine class compound, guanidine compound, azo-compound; And/or wherein said first char-forming agent and the second char-forming agent are selected from independently of one another: amylose starch, amylopectin, cyclodextrin, saccharide compound and polyhydric alcohol amine compounds; And/or wherein said phosphorization reagent is red phosphorus, Vanadium Pentoxide in FLAKES, phosphoric acid, tetra-sodium, polyphosphoric acid, phosphamide, poly-phosphamide or phosphorus oxychloride; And/or wherein said hydroxyl polyfunctional crosslinking agent be ethylene glycol, glycerine, tetramethylolmethane, mesitylene phenol, Resorcinol, monoethanolamine, aminopropanol or alcamine compound.
4. phosphorus-nitrogen expanding fire retardant according to claim 2, wherein the ratio of each composition is with described fire retardant main body: described first containing nitrogen blowing agent: described first char-forming agent counts 1-3: 0.5-1.5: 0.2-1.2.
5. phosphorus-nitrogen expanding fire retardant according to claim 1, wherein said phosphorization reagent and the described second weight ratio containing nitrogen blowing agent are 1: 0.5 to 1: 4.0; And/or the weight ratio of wherein said phosphorization reagent and described second char-forming agent is 1: 0.5 to 1: 3.0; And/or the weight ratio of wherein said phosphorization reagent and described hydroxyl polyfunctional crosslinking agent is 1: 0.5 to 1: 4.0; And/or the granular size of wherein said fire retardant is 0.4-20.0 micron; And/or the phosphorus content of wherein said fire retardant is 8-23%; And/or the nitrogen content of wherein said fire retardant is 10-34%.
6. prepare a method for phosphorus-nitrogen expanding fire retardant, said method comprising the steps of:
A) fire retardant main body preparation process, wherein makes phosphorization reagent, second containing nitrogen blowing agent, the second char-forming agent and hydroxyl polyfunctional crosslinking agent reaction, to obtain the reaction system containing fire retardant main body;
B) filtration step, wherein leaches the solid in above reaction system, to obtain fire retardant main body;
C) mixing step, wherein mixes described fire retardant main body containing nitrogen blowing agent and the first char-forming agent with first.
7. according to the method preparing phosphorus-nitrogen expanding fire retardant that claim 6 is stated, wherein in described fire retardant main body preparation process, first make described phosphorization reagent and described second react under the existence of initiator containing nitrogen blowing agent, add described second char-forming agent and described hydroxyl polyfunctional crosslinking agent afterwards.
8. a fire retarding paint, described fire retarding paint comprises the phosphorus-nitrogen expanding fire retardant described in any one in main body paint and claim 1-5.
9. the purposes of phosphorus-nitrogen expanding fire retardant in timber, cotton and paper are fire-retardant described in any one in claim 1-5.
10. fire retarding wood, flame-retardant cotton or a fire retardant papers, described fire retarding wood, flame-retardant cotton or fire retardant papers contain the phosphorus-nitrogen expanding fire retardant described in any one in claim 1-5.
CN201310535798.5A 2013-11-01 2013-11-01 Phosphorus-nitrogen expanding fire retardant, its synthetic method and its application Active CN104610794B (en)

Priority Applications (4)

Application Number Priority Date Filing Date Title
CN201310535798.5A CN104610794B (en) 2013-11-01 2013-11-01 Phosphorus-nitrogen expanding fire retardant, its synthetic method and its application
US15/032,537 US10301548B2 (en) 2013-11-01 2014-05-23 Phosphorus-nitrogen-based intumescent flame retardant and synthetic method and use thereof
PCT/CN2014/078258 WO2015062257A1 (en) 2013-11-01 2014-05-23 Phosphorus-nitrogen intumescent flame retardant, synthesis method therefor and use thereof
JP2016550914A JP6338681B2 (en) 2013-11-01 2014-05-23 Phosphorus-nitrogen based expansive flame retardant, synthesis method thereof, and use thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201310535798.5A CN104610794B (en) 2013-11-01 2013-11-01 Phosphorus-nitrogen expanding fire retardant, its synthetic method and its application

Publications (2)

Publication Number Publication Date
CN104610794A true CN104610794A (en) 2015-05-13
CN104610794B CN104610794B (en) 2017-07-11

Family

ID=53003250

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201310535798.5A Active CN104610794B (en) 2013-11-01 2013-11-01 Phosphorus-nitrogen expanding fire retardant, its synthetic method and its application

Country Status (4)

Country Link
US (1) US10301548B2 (en)
JP (1) JP6338681B2 (en)
CN (1) CN104610794B (en)
WO (1) WO2015062257A1 (en)

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105040432A (en) * 2015-06-18 2015-11-11 公安部四川消防研究所 Cross-linkable formaldehyde-free flame-retardant finishing agent and cotton fabric subjected to flame-retardant finishing by cross-linkable formaldehyde-free flame-retardant finishing agent
CN106884322A (en) * 2017-04-06 2017-06-23 天津工业大学 A kind of preparation method of flame-resistant polyacrylonitrile fiber
CN107298914A (en) * 2017-06-29 2017-10-27 陕西邦希化工有限公司 A kind of aqueous woodware paint and preparation method thereof
CN107513330A (en) * 2016-08-03 2017-12-26 韶关市连邦环保新材料股份有限公司 A kind of fireproof coating for steel construction and preparation method thereof
CN107857938A (en) * 2017-11-29 2018-03-30 宁波海雨新材料科技有限公司 A kind of halogen-free anti-flaming polypropylene material and its preparation method and application
CN107901162A (en) * 2017-10-20 2018-04-13 南宁科天水性科技有限责任公司 A kind of water-based fire retardant glued board environment-friendly type composite flame-retardant agent, water-based fire retardant glued board, preparation method and application
CN111185976A (en) * 2020-02-17 2020-05-22 成都艺听电子商务有限公司 Solid wood resin material and preparation method thereof
CN112029156A (en) * 2020-08-06 2020-12-04 湖北工程学院 Starch composite ammonium polyphosphate intumescent flame retardant and preparation method and application thereof
CN112211031A (en) * 2019-07-12 2021-01-12 中国科学院理化技术研究所 Preparation method of cellulose-based flame retardant and flame-retardant paper
WO2021097661A1 (en) * 2019-11-19 2021-05-27 南京先进生物材料与过程装备研究院有限公司 Special flame-retardant polypropylene for battery pack upper cover of new energy vehicle
CN113214116A (en) * 2021-05-08 2021-08-06 兰州大学 Preparation of phosphorus-nitrogen type flame retardant and application of phosphorus-nitrogen type flame retardant in anti-aging flame-retardant composite material
CN113265170A (en) * 2021-05-12 2021-08-17 贵州八六三科技有限公司 Flame retardant for environment-friendly paint
CN114736629A (en) * 2022-01-27 2022-07-12 浙江中聚材料有限公司 High-barrier flame-retardant back plate and preparation method thereof
CN116102835A (en) * 2023-01-08 2023-05-12 江苏中煜橡塑科技有限公司 Flame-retardant high-temperature-resistant fluororubber for sodium battery and processing technology thereof

Families Citing this family (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BR112018010145A2 (en) 2015-11-18 2019-02-05 Corning Optical Communications LLC flame retardant compound including host-guest complex
KR20180004477A (en) * 2016-07-04 2018-01-12 현대자동차주식회사 Flame Retardant for treating Kapok-fiber or Kapok-Nonwoven
WO2018227458A1 (en) * 2017-06-15 2018-12-20 Ppg Coatings (Kunshan) Co., Ltd. Intumescent coating composition
WO2019027882A1 (en) 2017-08-01 2019-02-07 Corning Incorporated Cyclodextrin-polyoxometalate ionic liquid inclusion complex flame retardant additive for making a low smoke zero halogen compound
CN108359149A (en) * 2018-02-10 2018-08-03 石磊 A kind of preparation method of expansion type flame-proof rubber
CN112323159B (en) * 2020-11-03 2022-09-06 宁波丹盈服饰有限公司 Flame-retardant lyocell fiber and preparation method thereof
CN112625244B (en) * 2020-12-30 2023-02-28 山东天一化学股份有限公司 Hyperbranched phosphorus-containing organic silicon intumescent flame retardant, preparation method and flame-retardant polymer coating composition
CN113637160B (en) * 2021-07-19 2023-09-19 武汉理工大学 Triazine structure-containing phosphorus-nitrogen star flame retardant, and preparation method and application thereof
CN115256576B (en) * 2022-06-23 2023-05-23 德华兔宝宝装饰新材股份有限公司 Treatment method of wood veneer, wood veneer and anti-rust flame-retardant plywood
CN115850712B (en) * 2022-11-30 2024-05-24 国网安徽省电力有限公司亳州供电公司 Phosphorus-nitrogen intumescent flame-retardant resin, preparation method thereof and application thereof in special paint for electric equipment and equipment
CN116330793B (en) * 2023-03-14 2023-09-26 南通北风橡塑制品有限公司 High-temperature-resistant flame-retardant polyurethane composite board and processing technology thereof

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4198328A (en) * 1977-10-10 1980-04-15 Montedison S.P.A. Flame-resisting intumescent paints
CN1114332A (en) * 1994-07-01 1996-01-03 中国科学技术大学 Halogen-free organophosphorous fire retardant, preparing process thereof and use for fire retarding paint
WO2001029123A1 (en) * 1999-10-21 2001-04-26 Ppg Industries Ohio, Inc. Fire retardant composition for composites
CN1807552A (en) * 2006-02-09 2006-07-26 朱凯琴 Novel phosphor nitrogen composite combustion inhibitor
CN101280197A (en) * 2008-05-06 2008-10-08 河北大学 Preparation of water-resistant expansion type flame retardant
CN102558617A (en) * 2011-12-23 2012-07-11 中国科学技术大学 Intumescent flame retardant and preparation method thereof
CN102719119A (en) * 2012-06-15 2012-10-10 公安部四川消防研究所 Novel intumescence powder steel structured fireproof paint and preparation method thereof

Family Cites Families (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS4937809B1 (en) * 1970-12-29 1974-10-12
JPS4932927A (en) * 1972-07-27 1974-03-26
JPS542220B2 (en) * 1974-03-06 1979-02-03
JPS5396038A (en) * 1977-02-03 1978-08-22 Dainippon Toryo Co Ltd Intumescent coating for electric wire
JPS56151776A (en) * 1980-04-25 1981-11-24 Hitachi Cable Ltd Foaming fire-proofing coating composition
US5387655A (en) * 1991-09-09 1995-02-07 Chemische Fabrik Budenheim Composition with integral intumescence properties
JP2003238902A (en) * 2002-02-22 2003-08-27 Kowa Chem Ind Co Ltd Composition for intumescent fireproof coating for indoor use
JP4675054B2 (en) * 2003-03-31 2011-04-20 エスケー化研株式会社 Foam fireproof paint
GB2401367B (en) * 2003-05-09 2007-12-19 Prometheus Developments Ltd Polymeric materials comprising cross-linked oligomers of diorthophosphate diesters
NL1033957C2 (en) * 2007-06-08 2008-12-09 Finifire B V Fire retardant and fire resistant composition.
JP2011052192A (en) * 2009-09-04 2011-03-17 Kaneka Corp Intumescent fireproof composition
CN102504645A (en) * 2011-11-03 2012-06-20 中国科学技术大学 Halogen-free organic phosphorus-nitrogen expandable flame retardant and application thereof to flame-retardant paint

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4198328A (en) * 1977-10-10 1980-04-15 Montedison S.P.A. Flame-resisting intumescent paints
CN1114332A (en) * 1994-07-01 1996-01-03 中国科学技术大学 Halogen-free organophosphorous fire retardant, preparing process thereof and use for fire retarding paint
WO2001029123A1 (en) * 1999-10-21 2001-04-26 Ppg Industries Ohio, Inc. Fire retardant composition for composites
CN1807552A (en) * 2006-02-09 2006-07-26 朱凯琴 Novel phosphor nitrogen composite combustion inhibitor
CN101280197A (en) * 2008-05-06 2008-10-08 河北大学 Preparation of water-resistant expansion type flame retardant
CN102558617A (en) * 2011-12-23 2012-07-11 中国科学技术大学 Intumescent flame retardant and preparation method thereof
CN102719119A (en) * 2012-06-15 2012-10-10 公安部四川消防研究所 Novel intumescence powder steel structured fireproof paint and preparation method thereof

Cited By (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105040432A (en) * 2015-06-18 2015-11-11 公安部四川消防研究所 Cross-linkable formaldehyde-free flame-retardant finishing agent and cotton fabric subjected to flame-retardant finishing by cross-linkable formaldehyde-free flame-retardant finishing agent
CN107513330A (en) * 2016-08-03 2017-12-26 韶关市连邦环保新材料股份有限公司 A kind of fireproof coating for steel construction and preparation method thereof
CN106884322A (en) * 2017-04-06 2017-06-23 天津工业大学 A kind of preparation method of flame-resistant polyacrylonitrile fiber
CN107298914A (en) * 2017-06-29 2017-10-27 陕西邦希化工有限公司 A kind of aqueous woodware paint and preparation method thereof
CN107901162A (en) * 2017-10-20 2018-04-13 南宁科天水性科技有限责任公司 A kind of water-based fire retardant glued board environment-friendly type composite flame-retardant agent, water-based fire retardant glued board, preparation method and application
CN107857938A (en) * 2017-11-29 2018-03-30 宁波海雨新材料科技有限公司 A kind of halogen-free anti-flaming polypropylene material and its preparation method and application
CN112211031A (en) * 2019-07-12 2021-01-12 中国科学院理化技术研究所 Preparation method of cellulose-based flame retardant and flame-retardant paper
WO2021097661A1 (en) * 2019-11-19 2021-05-27 南京先进生物材料与过程装备研究院有限公司 Special flame-retardant polypropylene for battery pack upper cover of new energy vehicle
CN111185976A (en) * 2020-02-17 2020-05-22 成都艺听电子商务有限公司 Solid wood resin material and preparation method thereof
CN112029156A (en) * 2020-08-06 2020-12-04 湖北工程学院 Starch composite ammonium polyphosphate intumescent flame retardant and preparation method and application thereof
CN112029156B (en) * 2020-08-06 2022-03-22 湖北工程学院 Starch composite ammonium polyphosphate intumescent flame retardant and preparation method and application thereof
CN113214116A (en) * 2021-05-08 2021-08-06 兰州大学 Preparation of phosphorus-nitrogen type flame retardant and application of phosphorus-nitrogen type flame retardant in anti-aging flame-retardant composite material
CN113265170A (en) * 2021-05-12 2021-08-17 贵州八六三科技有限公司 Flame retardant for environment-friendly paint
CN114736629A (en) * 2022-01-27 2022-07-12 浙江中聚材料有限公司 High-barrier flame-retardant back plate and preparation method thereof
CN114736629B (en) * 2022-01-27 2024-02-27 浙江中聚材料有限公司 High-barrier flame-retardant backboard and preparation method thereof
CN116102835A (en) * 2023-01-08 2023-05-12 江苏中煜橡塑科技有限公司 Flame-retardant high-temperature-resistant fluororubber for sodium battery and processing technology thereof
CN116102835B (en) * 2023-01-08 2024-03-19 江苏中煜橡塑科技有限公司 Flame-retardant high-temperature-resistant fluororubber for sodium battery and processing technology thereof

Also Published As

Publication number Publication date
CN104610794B (en) 2017-07-11
JP2016540874A (en) 2016-12-28
WO2015062257A1 (en) 2015-05-07
US10301548B2 (en) 2019-05-28
JP6338681B2 (en) 2018-06-06
US20160272892A1 (en) 2016-09-22

Similar Documents

Publication Publication Date Title
CN104610794A (en) Phosphor-nitrogen intumescent flame retardant, and synthetic method and applications thereof
CN104130671B (en) A kind of aqueous ultra-thin expansion type fireproof coating for steel construction and preparation method thereof
US3513114A (en) Intumescent coating compositions
CN109370288B (en) Intumescent water-based fireproof flame-retardant coating for wood material and preparation method thereof
CN101117510B (en) Modified amino resin expansion type aqueous flame-proof paint
CN102585347B (en) Halogen-free intumescent flame-retardant polypropylene mixture and preparation method thereof
CA2736682A1 (en) Fire retardant composition
CN106752681A (en) A kind of Water-borne inflation type refractory coating based on modified graphene oxide and preparation method thereof
WO2014090105A1 (en) Water-based expandable fireproof coating for steel structure and preparation method therefor
CN111732885B (en) Waterborne elastic polyurethane flame-retardant coating and preparation method thereof
CN102975251B (en) Flame retardant for wood as well as preparation method and applications of flame retardant for wood
CN108485351B (en) Modified hydrotalcite-based water-based smoke suppression expansion type fireproof coating and preparation method thereof
CN104559679A (en) Water-based waterproof coating added with calcium sulfate whiskers and preparation method of coating
CN110305551A (en) Novel aqueous intumescent paints and preparation method thereof
CN102975250B (en) Wood modifier and preparation method thereof
CN102277030A (en) Efficient environment-friendly flame retardant for flame retardance of coating and preparation method thereof
CN101838482A (en) Expansion type fireproof coating with zero content of volatile organic compound and low total smoke release amount in burning
CN108342133B (en) Method for preparing perchloroethylene fire-retardant coating by using loaded amine perlite as flame retardant
CN102423940B (en) Non-combustible compact plate and preparation method thereof
CN105085926B (en) The synthesis of transparent organophosphor-nitrogen high molecular weight flame retardant and its application in celluloid paint and varnish are fire-retardant
CN102975252B (en) Wood treatment agent and preparation method thereof
CN104610525A (en) Halogen-free environment-friendly polyurethane oil paint and preparation method thereof
CN102051104A (en) Fire-proof and anti-corrosive compatible paint with ultrathin expansion structure and production method thereof
CN109401406B (en) Intumescent smoke-suppressing fire retardant for water-based paint and preparation method thereof
CN102975253B (en) Wood fire retardant, preparation method and applications thereof

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant